KR20190049491A - Hetero-cyclic compound and organic light emitting device comprising same - Google Patents

Abstract

The present invention relates to a heterocyclic compound, capable of realizing low voltage, high efficiency and/or long lifetime of a device, and to an organic light emitting device including the same. The heterocyclic compound of the present invention is represented by chemical formula 1. In chemical formula 1, one of X1 and X2 is CRaRb and the other is a direct bond, and Ra and Rb are the same or different, and are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

Description

[0001] HETERO-CYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING SAME [0002]

This application claims the benefit of Korean Patent Application No. 10-2017-0142593 filed on October 30, 2017, filed with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

The present invention relates to a heterocyclic compound and an organic light emitting device including the same.

The organic light emission phenomenon is one example in which current is converted into visible light by an internal process of a specific organic molecule. The principle of organic luminescence phenomenon is as follows. When an organic layer is positioned between an anode and a cathode, when a voltage is applied between the two electrodes, electrons and holes are injected into the organic layer from the cathode and the anode, respectively. Electrons and holes injected into the organic material layer recombine in the light emitting layer to form a molecular exiton as an electron-hole pair, and the exciton falls back to a low ground state to emit light . An organic light emitting device using such a principle may be generally composed of an organic material layer including a cathode, an anode, and an organic material layer disposed therebetween, for example, a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer.

Here, the light emitting layer is composed of only the light emitting material or has a structure including a very small amount of the light emitting material (dopant). When a light emitting material is included, a material containing a light emitting material is referred to as a host material or a matrix material, and a light emitting material is referred to as a dopant or guest material. The light emitting material enhances the efficiency of the organic light emitting device by generating more photons from the excitons and has a variety of colors for each light emitting material, thereby playing an advantageous role in controlling the color of the organic light emitting device.

KR 10-2005-0084398 A

The present invention aims to provide a heterocyclic compound capable of realizing low voltage, high efficiency and / or high durability of a device.

The present invention provides a heterocyclic compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

One of X1 and X2 is CRaRb and the other is a direct bond,

Ra and Rb are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

One of X3 and X4 is S or O and the other is a direct bond,

One of A and B is substituted or unsubstituted benzene and the other is substituted or substituted naphthalene,

Ar is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

R1 and R2 are the same as or different from each other, and each independently selected from the group consisting of deuterium; A halogen group; A nitrile group; A nitro group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; Substituted or unsubstituted -O (R10); Substituted or unsubstituted -Si (R11) (R12) (R13); A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; Or substituted or unsubstituted -N (R14) (R15), or is bonded to an adjacent group to form a ring,

R10 to R15 are the same or different from each other and each independently hydrogen; heavy hydrogen; An alkyl group; Or an aryl group,

a1 is an integer of 0 to 4; when a1 is 2 or more, R1 is the same as or different from each other,

a2 is an integer of 0 to 4, and when a2 is 2 or more, R2 is the same as or different from each other.

The organic electroluminescent device according to the present invention includes a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein the organic material layer includes the above-mentioned heterocyclic compound A light emitting device is provided.

When the heterocyclic compound according to one embodiment of the present invention is used in an organic light emitting device, the efficiency, driving voltage and / or lifetime characteristics of the device are improved.

In one embodiment, the heterocyclic compound of the present invention can be used as a host material in an organic light emitting device.

Fig. 1 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a light emitting layer 8 and a cathode 4. [
FIG. 2 is a cross-sectional view schematically showing the structure of a substrate 1, an anode 2, a first hole injecting layer 5, a second hole injecting layer 9, a hole transporting layer 6, a hole adjusting layer 7, An organic electroluminescent device comprising a transport layer 10, an electron injection layer 11 and a cathode 4 is shown.

Hereinafter, the present invention will be described in more detail.

Illustrative examples of such substituents are set forth below, but are not limited thereto.

As used herein, the term " substituted " A halogen group; A nitrile group; A nitro group; An alkyl group; A cycloalkyl group; An alkenyl group; -O (R51); -Si (R52) (R53) (R54); An aryl group; A heteroaryl group; And -N (R55) (R56), or two or more groups selected from the group may be substituted with a group to which they are connected, or two or more groups selected from the group may be substituted, and two adjacent groups may be bonded to each other To form a ring. Here, R51 to R56 are the same or different from each other, and each independently hydrogen; heavy hydrogen; An alkyl group; An aryl group; Or a heteroaryl group.

The term " a group to which two or more groups are connected " means a group in which two or more groups are linked by a covalent bond. For example, two groups of attached groups include alkylaryl groups; A cycloalkylaryl group; An alkylamine group; A heteroarylamine group, and the like. For example, a group in which three groups are connected includes a 4-methyl-2-phenyldibenzofuranyl group; 2-nitro-2-cyclohexylpentyl, and the like.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec- , n-hexyl, 1-methylpentyl, 2-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, Octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, Hexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group means a cyclic saturated hydrocarbon group. The number of carbon atoms is not particularly limited, but is preferably 3 to 60, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the alkenyl group represents an unsaturated hydrocarbon group, and may be linear or branched. The number of carbon atoms is not particularly limited, but is preferably from 2 to 30. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. Specific examples include, but are not limited to, ethenyl, vinyl, propenyl, allyl, isopropenyl, butenyl, isobutenyl, 3-pentenyl and 2-hexenyl.

In the present specification, -Si (R52) (R53) (R54) specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, Diphenylsilyl group, phenylsilyl group, and the like, but is not limited thereto

In the present specification, an aryl group means a substituted or unsubstituted monocyclic or polycyclic, wholly or partially unsaturated. The number of carbon atoms is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 40 carbon atoms. According to one embodiment, the aryl group has 6 to 30 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a klycenyl group, a fluorenyl group and a triphenylrenyl group.

In the present specification, when it is assumed that the fluorenyl group can be substituted, the substituted fluorenyl group encompasses all of the compounds wherein the substituents on the pentagonal ring of the fluorenyl group are spiro bonded to each other to form aromatic hydrocarbons. The substituted fluorenes include 9,9'-spirobifluorene, spiro [cyclopentane-1,9'-fluorene], spiro [benzo [c] fluorene-7,9-fluorene] , But is not limited thereto.

In the present specification, the heteroaryl group is an aryl group containing at least one of N, O, S and Se as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. According to one embodiment, the heteroaryl group has 2 to 40 carbon atoms. According to another embodiment, the heteroaryl group has 2 to 30 carbon atoms. Examples of the heteroaryl group include a thiophenyl group, a furanyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a triazolyl group, a pyridinyl group, a bipyridinyl group, a pyrimidinyl group, A thienyl group, a thienyl group, a thienyl group, a thienyl group, a thiazolyl group, a thiazolyl group, an acridinyl group, a carbolinyl group, an acenaphthoquinoxalinyl group, an indenoquinazolinyl group, an indenoisoquinolinyl group, A pyrimidinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyranyl group, a pyrazinopyrazinyl group, an isoquinolinyl group, , A benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a benzocarbazolyl group, a benzothiophenyl group, a dibenzothiophenyl group, a benzofuranyl group, a dibenzofuranyl group, a phenanthrolinyl group, An isoxazolyl group, an oxadiazolyl group, Oh thiadiazolyl group, but include benzothiazolyl group, a page group, and a phenothiazine noksa possess thiazinyl group, but are not limited thereto.

As used herein, the term " adjacent " means that the substituent is a substituent substituted on an atom directly connected to the substituted atom, a substituent stereostructically closest to the substituent, or another substituent substituted on the substituted atom . For example, two substituents substituted at the ortho position in the benzene ring and two substituents substituted at the same carbon in the aliphatic ring may be interpreted as adjacent groups.

In the present specification, the term " forming a ring by bonding with adjacent groups " means a substituted or unsubstituted aliphatic hydrocarbon ring bonded to adjacent groups to form a ring; A substituted or unsubstituted aromatic hydrocarbon ring; A substituted or unsubstituted aliphatic heterocycle; A substituted or unsubstituted aromatic heterocycle; Or a condensed ring thereof.

In the present specification, an aliphatic hydrocarbon ring means a ring which is a non-aromatic ring and consists only of carbon and hydrogen atoms.

As used herein, the term " aromatic ring " means a ring having aromatic hydrocarbon rings only and consisting of only carbon and hydrogen atoms. Examples include, but are not limited to, a phenyl group, a naphthyl group, and an anthracenyl group.

In the present specification, an aliphatic heterocyclic ring means an aliphatic ring containing at least one hetero atom.

As used herein, an aromatic heterocyclic ring means an aromatic ring containing at least one heteroatom.

는 다른 치환기에 연결되는 부위를 의미한다.In the present specification,

Quot; refers to a moiety that is connected to another substituent.

One embodiment of the present invention provides a heterocyclic compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

One of X1 and X2 is CRaRb and the other is a direct bond,

Ra and Rb are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

One of X3 and X4 is S or O and the other is a direct bond,

One of A and B is substituted or unsubstituted benzene and the other is substituted or substituted naphthalene,

Ar is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

R1 and R2 are the same as or different from each other, and each independently selected from the group consisting of deuterium; A halogen group; A nitrile group; A nitro group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; Substituted or unsubstituted -O (R10); Substituted or unsubstituted -Si (R11) (R12) (R13); A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; Or substituted or unsubstituted -N (R14) (R15), or is bonded to an adjacent group to form a ring,

R10 to R15 are the same or different from each other and each independently hydrogen; heavy hydrogen; An alkyl group; Or an aryl group,

a1 is an integer of 0 to 4; when a1 is 2 or more, R1 is the same as or different from each other,

a2 is an integer of 0 to 4, and when a2 is 2 or more, R2 is the same as or different from each other.

)과 전자 주개(electron donor) 부분(

)으로 구성되며, 화학식 1의 화합물은 상기 전자 주개 부분과 전자 받개 부분이 직접 연결됨으로써 화합물의 밴드갭이 줄어들어, 발광층의 호스트 재료로 사용될 수 있다.In the present invention, the chemical formula 1 is an electron acceptor

) And the electron donor portion (

The compound of formula (1) can be used as a host material for the light emitting layer by reducing the bandgap of the compound by directly connecting the electron donor part and the electron acceptor part.

In one embodiment, the compound represented by Formula 1 may be used as a host material of the red light emitting layer.

In one embodiment, the formula (1) may be represented by any one of the following formulas (2) to (4).

(2)

(3)

[Chemical Formula 4]

In the above formulas 2 to 4,

X1, X2, X3, X4, R1, R2, Ar, a1 and a2 are as defined in formula (1)

R3 to R6 are the same as or different from each other, and each independently selected from the group consisting of deuterium; A halogen group; A nitrile group; A nitro group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; Substituted or unsubstituted-O (R16); Substituted or unsubstituted -Si (R17) (R18) (R19); A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; Or substituted or unsubstituted -N (R20) (R21), or is bonded to an adjacent group to form a ring,

R16 to R21 are the same or different from each other, and each independently hydrogen; heavy hydrogen; An alkyl group; Or an aryl group,

a3 is an integer of 0 to 2, and when a3 is 2, R3 is the same as or different from each other,

a4 is an integer of 0 to 6, and when a4 is 2 or more, R4 is the same or different from each other,

a5 is an integer of 0 to 6, and when a5 is 2 or more, R5 are the same as or different from each other,

a6 is an integer of 0 to 6, and when a6 is 2 or more, R6 is the same as or different from each other.

According to one embodiment of the present invention, the formula (2) is represented by any one of the following formulas (2-1) to (2-3).

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In the general formulas (2-1) to (2-3)

X1 to X4, R1 to R3, R6, Ar, a1 to a3 and a6 are as defined in formula (2).

According to one embodiment of the present invention, the formula (3) is represented by any one of the following formulas (3-1) to (3-3).

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

In the above formulas (3-1) to (3-3)

X1 to X4, R1 to R4, Ar and a1 to a4 are the same as defined in formula (3).

According to one embodiment of the present invention, the formula (4) is represented by any one of the following formulas (4-1) to (4-3).

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

In Formulas 4-1 to 4-3,

X1 to X4, R1 to R3, R5, Ar, a1 to a3 and a5 are as defined in formula (4).

According to one embodiment of the present invention, the formula (1) is represented by the following formula (5) or (6).

[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas (5) and (6)

X1 to X4, R1, R2, a1, a2 and Ar are as defined in the formula (1)

R7 to R9 are the same as or different from each other, and each independently selected from the group consisting of deuterium; A halogen group; A nitrile group; A nitro group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; Substituted or unsubstituted -O (R22); Substituted or unsubstituted -Si (R23) (R24) (R25); A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; Or substituted or unsubstituted -N (R26) (R27), or combine with adjacent groups to form a ring,

R22 to R27 are the same or different from each other and each independently hydrogen; heavy hydrogen; An alkyl group; Or an aryl group,

a7 is an integer of 0 to 4, and when a7 is 2 or more, R7 is the same as or different from each other,

a8 is an integer of 0 to 4, and when a8 is 2 or more, R8 are the same as or different from each other,

a9 is an integer of 0 to 4, and when a9 is 2 or more, R9 is the same as or different from each other.

According to one embodiment of the present invention, X1 is a direct bond and X2 is CRaRb.

According to one embodiment of the present invention, X1 is CRaRb and X2 is a direct bond.

According to one embodiment of the present invention, X1 of X1 and X2 binds to the benzene ring more closely to N.

According to an embodiment of the present invention, Ra and Rb are the same or different from each other and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.

According to one embodiment of the present invention, Ra and Rb are substituted or unsubstituted C1-C10 alkyl groups.

According to one embodiment of the present invention, Ra and Rb are substituted or unsubstituted C1-C6 alkyl groups.

According to one embodiment of the present invention, Ra and Rb are substituted or unsubstituted C1-C4 alkyl groups.

According to one embodiment of the present invention, Ra and Rb are alkyl groups.

According to one embodiment of the present invention, Ra is a methyl group.

According to one embodiment of the present invention, Rb is a methyl group.

According to one embodiment of the present invention, one of X3 and X4 is S or O and the other is a direct bond. Wherein X3 or X4 is CH ₂ it is highly unstable compound. When X3 or X4 is C (R60) (R61) and R60 and R61 are each independently an alkyl group or an aryl group, the lifetime of the device is lowered due to steric hindrance between R60 and R61 and Ar. Therefore, among X3 and X4 One of them is preferably S or O. [

According to one embodiment of the present invention, X3 is S and X4 is a direct bond.

According to one embodiment of the present invention, X3 is O and X4 is a direct bond.

According to one embodiment of the present invention, R1 is hydrogen.

According to one embodiment of the present invention, R2 is hydrogen.

According to one embodiment of the present invention, R3 is hydrogen.

According to one embodiment of the present invention, R4 is hydrogen.

According to one embodiment of the present invention, R5 is hydrogen.

According to one embodiment of the present invention, R6 is hydrogen.

According to an embodiment of the present invention, R7 is hydrogen.

According to one embodiment of the present invention, R8 is hydrogen.

According to one embodiment of the present invention, R9 is hydrogen.

According to one embodiment of the present invention, a1 is zero.

According to one embodiment of the present invention, a2 is zero.

According to one embodiment of the present invention, a3 is zero.

According to one embodiment of the present invention, a4 is zero.

According to one embodiment of the present invention, a5 is zero.

According to one embodiment of the present invention, a6 is zero.

According to one embodiment of the present invention, a7 is 0.

According to one embodiment of the present invention, the a8 is zero.

According to an embodiment of the present invention, a9 is 0.

According to one embodiment of the present invention, A is naphthalene and B is benzene.

According to one embodiment of the present invention, A is benzene and B is naphthalene.

According to one embodiment of the present invention, Ar is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

According to one embodiment of the present invention, Ar is a substituted or unsubstituted C6-C25 aryl group; Or a substituted or unsubstituted C2-C25 heteroaryl group.

According to one embodiment of the present invention, Ar is a substituted or unsubstituted C6-C18 aryl group; Or a substituted or unsubstituted C2-C20 heteroaryl group.

According to one embodiment of the present invention, Ar is an aryl group substituted or unsubstituted with an alkyl group or an aryl group; Or a heteroaryl group substituted or unsubstituted with an alkyl group or an aryl group.

According to one embodiment of the present invention, Ar is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted dibenzofuranyl group; A substituted or unsubstituted dibenzothiophenyl group; Or a substituted or unsubstituted carbazolyl group.

According to one embodiment of the present invention, Ar is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted naphthyl group; A dibenzofuranyl group substituted or unsubstituted with an aryl group; A dibenzofuranyl group substituted or unsubstituted with an aryl group; Or a carbazolyl group substituted or unsubstituted with an aryl group.

According to one embodiment of the present invention, Ar represents a phenyl group; A biphenyl group; Naphthyl group; A dibenzofuranyl group; A dibenzothiophenyl group; Or a carbazolyl group substituted or unsubstituted with a phenyl group.

According to one embodiment of the present invention, the heterocyclic compound represented by Formula 1 is any one selected from the following heterocyclic compounds.

According to an embodiment of the present invention, the heterocyclic compound represented by the above-mentioned formula (1) can be prepared in the same manner as in the following reaction formula (1).

[Reaction Scheme 1]

In the above Reaction Scheme 1, the definitions of A, B, X1, X2, X3, X4, R1, R2, Ar, a1 and a2 are as defined in Formula 1, and X and X 'are each independently a halogen group. In the present invention, the heterocyclic compound represented by Formula 1 may be synthesized through a Suzuki coupling reaction and a Buchwald-Hartwig amination reaction.

However, the synthesis method of Reaction Scheme 1 is only one example of the synthesis method of the heterocyclic compound represented by Chemical Formula 1, and it is possible to use a method in which some of the reagents are different in Reaction Scheme 1, some synthesis steps are different, The heterocyclic compound represented by the above formula (1) can be synthesized.

Also, the present invention provides an organic light emitting device comprising the heterocyclic compound represented by Formula 1.

According to an embodiment of the present invention, there is provided an organic light emitting device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, And a heterocyclic compound which is capable of reacting with an organic compound.

In one embodiment of the present invention, the second electrode is provided opposite to the first electrode.

The organic material layer of the organic light emitting device may have a single layer structure or a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a hole control layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may include fewer or larger numbers of organic layers.

In one embodiment of the present invention, the organic material layer includes at least one of a hole injection layer, a hole transport layer, a layer that simultaneously transports and injects holes, and a hole control layer, and the hole injection layer, the hole transport layer, And at least one of the layer and hole-regulating layer simultaneously injecting a heterocyclic compound represented by the above formula (1).

In one embodiment of the present invention, the organic layer includes a light emitting layer, and the light emitting layer includes a heterocyclic compound represented by the general formula (1).

In one embodiment of the present invention, the organic layer includes a light emitting layer, and the light emitting layer includes a heterocyclic compound represented by Formula 1 as a host.

In one embodiment of the present invention, the light emitting layer containing the heterocyclic compound represented by the general formula (1) may be a red light emitting layer.

In one embodiment of the present invention, the light emitting layer further includes a dopant.

In one embodiment of the present invention, the dopant may be a phosphorescent dopant or a fluorescent dopant.

The phosphorescent dopants are those conventionally used in the art and include tris (2-phenylpyridinato-N, C2) ruthenium, bis (2-phenylpyridinato-N, C2) palladium, bis (2-phenylpyridinato-N, C2) rhenium, octaethylplatinum porphyrin, octaphenylplatinum porphyrin, octaethyl (4,6-difluorophenyl) -pyridinate-N, C2 '] picolinate (Firpic), tris (2-phenylpyridinato- N, C2) iridium (Ir (ppy) _3), fac- tris (2-phenylpyridine) iridium (ⅲ) (fac-Ir ( ppy) 3), bis (2-phenylpyridinato -N Deen Sat, C2) Iridium (acetylacetonate) (Ir (ppy) ₂ (acac)) and 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphine platinum (II) But is not limited thereto.

Examples of the fluorescent dopant include Alq ₃ (tris (8-hydroxyquinolino) aluminum), spiro-DPVBi, spiro-6P, distyrylbenzene (DSB), distyrylarylene (DSA), PFO- Bis (diphenylamine) pyrene, tetrakis (t-butyl) perylene, p-bis (pN, N-diphenyl-aminostyryl) Pheny1 cyclopentadiene, and the like, but the present invention is not limited thereto.

In one embodiment of the present invention, the organic material layer includes at least one of an electron injecting layer and an electron transporting layer, and at least one of the electron injecting layer and the electron transporting layer contains a hetero ring ≪ / RTI >

In one embodiment of the present invention, the organic layer includes an electron control layer, and the electron control layer includes a heterocyclic compound represented by Formula 1. [

In one embodiment of the present invention, the organic material layer includes two or more hole injection layers.

In one embodiment of the present invention, the organic material layer includes a hole injecting layer, a hole transporting layer, a hole controlling layer, a light emitting layer, an electron transporting layer, and an electron injecting layer, and the light emitting layer includes a heterocyclic compound represented by Formula 1 .

In one embodiment of the present invention, the organic material layer includes a first hole injection layer, a second hole injection layer, a hole transport layer, a hole control layer, a light emitting layer, an electron transport layer and an electron injection layer, And a heterocyclic compound to be represented.

In one embodiment of the present invention, the first hole injection layer and the second hole injection layer may be the same or different from each other.

In one embodiment of the present invention, the organic material layer includes a hole injecting layer, a hole transporting layer, a hole controlling layer, a light emitting layer, and a layer simultaneously transporting and injecting electrons, wherein the light emitting layer comprises a heterocyclic compound represented by Formula 1 .

In one embodiment of the present invention, the organic light emitting device may be a normal type organic light emitting device in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate.

In one embodiment of the present invention, the organic light emitting device may be an inverted type organic light emitting device in which a cathode, at least one organic material layer, and an anode are sequentially stacked on a substrate.

In one embodiment of the present invention, the first electrode is an anode and the second electrode is a cathode.

In one embodiment of the present invention, the first electrode is a cathode and the second electrode is a cathode.

For example, the structure of the organic light emitting device according to one embodiment of the present disclosure is illustrated in FIGS.

Fig. 1 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a light emitting layer 8 and a cathode 4. [ In this structure, the heterocyclic compound represented by Formula 1 may be included in the light emitting layer 8.

FIG. 2 is a cross-sectional view schematically showing the structure of a substrate 1, an anode 2, a first hole injecting layer 5, a second hole injecting layer 9, a hole transporting layer 6, a hole adjusting layer 7, An organic electroluminescent device comprising a transport layer 10, an electron injection layer 11 and a cathode 4 is shown. In this structure, the heterocyclic compound represented by the formula (1) may be added to the first hole injection layer 5, the second hole injection layer 9, the hole transport layer 6, the light emitting layer 8, the electron transport layer 10, Or may be included in the electron injection layer 11.

The organic light emitting device of the present invention can be manufactured by materials and methods known in the art except that one or more of the organic layers include the compound of the present invention, i.e., the heterocyclic compound represented by the above formula (1).

When the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

For example, the organic light emitting device of the present invention can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as a sputtering method or an e-beam evaporation method, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate to form a positive electrode Forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and depositing a material usable as a cathode thereon. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

The heterocyclic compound represented by Formula 1 may be formed into an organic layer by a solution coating method as well as a vacuum deposition method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

In addition to such a method, an organic light emitting device may be formed by sequentially depositing an organic material layer and a cathode material from a cathode material on a substrate. However, the manufacturing method is not limited thereto.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole injection layer is a layer for injecting holes, which are received from the electrode, into an adjacent layer provided to the light emitting layer or the light emitting layer. The hole injecting material has a hole injecting effect on the anode, an excellent hole injecting effect on the light emitting layer or the light emitting material due to its ability to transport holes, and the migration of the excitons generated in the light emitting layer to the electron injecting layer or the electron injecting material It is preferable to use a compound having excellent ability to form a thin film. The highest occupied molecular orbital (HOMO) of the hole injecting material is preferably between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include organic materials such as metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene- Based organic materials, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emission layer. As the hole transporting material, a material capable of transporting holes from the anode or the hole injecting layer to the light emitting layer and having high mobility to holes is suitable. Specific examples of the hole transporting material include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but the present invention is not limited thereto.

The hole-adjusting layer is a light-emitting layer that prevents exciter electrons from entering the anode and regulates the performance of the entire device by controlling the flow of holes flowing into the light-emitting layer. The hole-controlling material is preferably a compound having an ability to prevent the flow of electrons from the light-emitting layer to the anode and to control the flow of holes injected into the light-emitting layer or the light-emitting material. In one embodiment, an arylamine-based organic material may be used as the electron blocking layer, but the present invention is not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Benzoxazole, benzothiazole and benzimidazole compounds; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds and fluoranthene compounds. Examples of heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material of the light emitting layer include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. As the aromatic amine derivative, a condensed aromatic ring derivative having a substituted or unsubstituted arylamine group may be used, such as pyrene, anthracene, klysene, and peripherrhene having an arylamine group. As the styrylamine compound, a compound in which substituted or unsubstituted arylamine is substituted with at least one aryl vinyl group can be used. Examples of the styrylamine compound include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. As the metal complex, an iridium complex, a platinum complex, or the like can be used, but it is not limited thereto.

The electron control layer is a layer that blocks the flow of holes from the light emitting layer into the cathode and adjusts the performance of the entire device by controlling electrons flowing into the light emitting layer. The electron control material is preferably a compound capable of preventing the inflow of holes from the light emitting layer to the cathode and controlling the electrons injected into the light emitting layer or the light emitting material. As the electron control material, an appropriate material may be used depending on the constitution of the organic material layer used in the device. The electron control layer is disposed between the light emitting layer and the cathode, and is preferably provided directly in contact with the light emitting layer.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emission layer. As the electron transporting material, a material capable of transferring electrons from the cathode well into the light emitting layer, which is suitable for electrons, is suitable. Examples of the electron transporting material include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In one embodiment, the negative electrode material comprises a material having a low work function; And an aluminum layer or a silver layer may be used. Examples of the material having the low work function include cesium, barium, calcium, ytterbium, and samarium. An aluminum layer or a silver layer may be formed on the layer after forming the layer with the material.

The electron injection layer is a layer for injecting electrons received from the electrode into the light emitting layer. The electron injecting material has an ability to transport electrons, has an electron injecting effect from the cathode, an electron injecting effect to the emitting layer or the light emitting material, prevents migration of excitons generated in the emitting layer to the hole injecting layer, Further, it is preferable to use a compound having excellent ability to form a thin film. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A complex compound and a nitrogen-containing five-membered ring derivative, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

The organic light emitting device according to the present invention may be of a top emission type, a back emission type, or a both-side emission type, depending on the material used.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

[Manufacturing Example]

Production Example 1: Preparation of Compound A

Preparation of Compound A-1

3-bromo-9,9-dimethyl-3-neck flask -9H- fluorene (20g, 73.2mmol), bis (pinacolato) diboron (22.3g, 87.9mmol), Pd ( dba) 2 (0.8g , Tricyclohexylphosphine (0.8 g, 2.9 mmol), KOAc (14.4 g, 146.6 mmol) and 300 ml of 1,4-dioxane were placed and stirred for 12 hours under reflux in an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, transferred to a separatory funnel, and extracted with water and ethyl acetate. The extract was dried with magnesium sulfate, filtered and concentrated. The sample was purified by silica gel column chromatography to obtain Compound A-1 (15.9 g, yield 68%, MS: [M + H] ⁺ = 320) .

Preparation of Compound A-2

Compound A-1 (15 g, 46.8 mmol) and 1-bromo-2-nitronaphthalene (13 g, 51.5 mmol) were dissolved in 225 ml of THF, and K ₂ CO ₃ (25.9 g, 187.4 mmol) . Here Pd (PPh ₃₎ into a ₄ (2.7g, 2.3mmol), followed by stirring for 8 hours in an argon atmosphere under reflux conditions. After the reaction was completed, the reaction solution was cooled to room temperature, transferred to a separatory funnel, and extracted with water and ethyl acetate. The extract was dried with MgSO ₄ , filtered and concentrated. The sample was purified by silica gel column chromatography to obtain Compound A-2 (13.9 g, yield 81%, MS [M + H] ⁺ = 365).

Preparation of Compound A

Compound A-2 (13 g, 35.6 mmol), triphenylphosphine (7.4 g, 53.4 mmol) and o-dichlorobenzene (130 mL) were placed in a two-necked flask and stirred under reflux conditions for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, distilled under reduced pressure to remove the solvent, and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated. The sample was purified by silica gel column chromatography to obtain Compound A (8.9 g, yield 75%, MS: [M + H] ⁺ = 333).

Preparation Example 2: Preparation of Compound (B)

Preparation of Compound B-1

Compound A-1 was prepared in the same manner as Compound A-1 except that 2-bromo-9,9-dimethyl-9H-fluorene was used instead of 3-bromo-9,9- -1 (MS: [M + H] < ⁺ > = 320).

Preparation of compound B-2

Compound B-2 was obtained in the same manner as Compound A-2 except that Compound B-1 was used instead of Compound A-1. MS: [M + H] ⁺ = 365.

Preparation of Compound B

Compound B was obtained in the same manner as Compound A, except that Compound B-2 was used instead of Compound A-2. MS: [M + H] ⁺ = 333.

Preparation Example 3: Preparation of Compound C

Preparation of Compound C-1

Compound C-1 was obtained in the same manner as Compound B-2 except that 2-bromo-1-nitronaphthalene was used instead of 1-bromo-2-nitronaphthalene (MS: [M + H] < ⁺ > = 365).

Preparation of Compound C

Compound C was obtained in the same manner as Compound A, except that Compound C-1 was used instead of Compound A-2. MS: [M + H] ⁺ = 333.

Preparation Example 4: Preparation of Compound (D)

Preparation of compound D-1

(15 g, 71.7 mmol) and 2,3-dibromonaphthalene (22.5 g, 78.8 mmol) were dissolved in toluene (300 mL) and sodium t -Butoxide (10.3 g, 107.5 mmol) and Pd (P (t-Bu) ₃ ) ₂ (0.7 g, 1.4 mmol) were added and stirred for 12 hours under argon atmosphere and refluxing conditions. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added, and the reaction solution was transferred to a separatory funnel. The extract was dried over MgSO ₄ and concentrated. The sample was purified by silica gel column chromatography to give 23.2 g (78% yield, MS: [M + H] ⁺ = 414).

Preparation of compound D

Compound D-1 (20 g, 48.3 mmol), triphenylphosphine (10 g, 72.4 mmol) and o-dichlorobenzene (200 mL) were placed in a two-necked flask and stirred under reflux conditions for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, distilled under reduced pressure to remove the solvent, and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated. The sample was purified by silica gel column chromatography to give compound D (12.1 g, yield 75%, MS: [M + H] ⁺ = 333).

Preparation Example 5: Preparation of Compound E

Preparation of Compound E-1

Compound E-1 was prepared in the same manner as Compound D-1 except that 9,9-dimethyl-9H-fluoren-4-amine was used instead of 9,9-dimethyl- (MS: [M + H] < ⁺ > = 414).

Preparation of Compound E

Compound E was obtained in the same manner as Compound D, except that Compound E-1 was used instead of Compound D-1. MS: [M + H] ⁺ = 333.

Preparation Example 6: Preparation of Compound F

Preparation of Compound F-1

Three-necked flask was charged with 2-bromo-4-chloro-1-nitro benzene (30g, 126.9mmol) and naphthalene-2-Daily acid (24g, 139.6mmol) was dissolved in _{THF (450mL) K 2 CO 3} (70.1 g, 507.5 mmol) was dissolved in water (150 mL). Here Pd (PPh ₃₎ into a ₄ (7.3g, 6.3mmol), and the mixture was stirred for 8 hours under reflux conditions in an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried over MgSO ₄ , filtered and concentrated, and then recrystallized with ethanol to obtain Compound F-1 (29.2 g, yield 81%, MS: [M + H] ⁺ = 283).

Preparation of Compound F-2

Compound F-1 (29 g, 102.2 mmol), triphenylphosphine (21.2 g, 153.3 mmol) and o-dichlorobenzene (290 mL) were placed in a two-necked flask and stirred under reflux conditions for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, distilled under reduced pressure to remove the solvent, and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated. The sample was purified by silica gel column chromatography to give compound F-2 (18.3 g, yield 71%, MS: [M + H] ⁺ = 251).

Preparation of Compound F-3

(18 g, 71.5 mmol) was dissolved in THF (180 mL) under nitrogen atmosphere, and a hexane solution (49 mL, 1.6 mL) containing n-butyllithium at a concentration of 1.6 M was added thereto while stirring at- 78.7 mmol) was slowly added dropwise. When the dropwise addition was completed, the solution was further stirred at -78 ° C for 1 hour. Thereafter, trimethylborate (8.9 g, 85.8 mmol) was slowly added dropwise, and then the mixture was stirred at room temperature for 1 hour. When the reaction was completed, 2N HCl aqueous solution (50 mL) was added dropwise at room temperature and stirred for 30 minutes. The reaction solution was transferred to a separatory funnel and the organic layer was extracted with water and ethyl acetate. The organic layer was concentrated under reduced pressure, and recrystallized from CH ₂ Cl ₂ and hexane to obtain Compound F-3 (12.7 g, yield 68% M + H] < ⁺ > = 261).

Preparation of Compound F-4

The compound F-3 (12 g, 46 mmol) and methyl-2-bromobenzoate (10.9 g, 50.6 mmol) were dissolved in THF (180 mL) and K ₂ CO ₃ (25.4 g, 183.8 mmol) 60 mL). Here Pd (PPh ₃₎ into a ₄ (2.7g, 2.3mmol), and the mixture was stirred for 8 hours under reflux conditions in an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, transferred to a separatory funnel, and extracted with ethyl acetate. The extract was dried with MgSO ₄ , filtered and concentrated, and then recrystallized with ethanol to obtain Compound (F-4) (13.9 g, yield 86%, MS: [M + H] ⁺ = 351).

Preparation of Compound F-5

To a dried two-necked flask, Compound F-4 (13 g, 37 mmol) was dissolved in THF (130 mL) under nitrogen atmosphere, and a hexane solution (58 mL, 92.5 mmol) I dropped it slowly. When the dropwise addition was completed, the reaction mixture was stirred at -78 ° C for 2 hours. Then, ethanol (30 ml) was added, the mixture was warmed to room temperature and stirred for 1 hour. After the reaction was completed, 100 ml of an aqueous sodium chloride solution was added and the mixture was stirred for 20 minutes. The reaction solution was transferred to a separatory funnel, and the organic layer was extracted with water and ethyl acetate. The filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain compound F- (8.8 g, yield 68%, MS: [M + H] < ⁺ > = 351).

Preparation of Compound F

Compound F-5 (8 g, 22.8 mmol) and acetic acid (160 ml) were added to a two-necked flask, and then concentrated sulfuric acid (0.3 ml) was slowly added thereto and stirred for 3 hours. After completion of the reaction, the reaction solution was poured into 500 ml of water, stirred for 30 minutes, transferred to a separatory funnel, extracted with chloroform, and washed with 300 ml of aqueous sodium chloride solution. The organic layer was dried over MgSO ₄ , filtered and concentrated. The sample was purified by silica gel column chromatography to obtain Compound F (6.5 g, yield 85%, MS: [M + H] ⁺ = 333).

Production Example 7: Preparation of Compound G

Preparation of Compound G-1

To a three-necked flask was added a solution of (7,7-dimethyl-7H-benzo [c] fluoren-5-yl) boronic acid (15g, 52.1mmol), 1- bromo-2-nitrobenzene (11.6g, 57.3mmol) Is dissolved in 225 ml of THF, and K ₂ CO ₃ (28.8 g, 208.2 mmol) is dissolved in 75 ml of water. Here Pd (PPh ₃₎ into a ₄ (3g, 2.6mmol), followed by stirring for 8 hours in an argon atmosphere under reflux conditions. After the reaction was completed, the reaction solution was cooled to room temperature, transferred to a separatory funnel, and extracted with water and ethyl acetate. The extract was dried with MgSO ₄ , filtered and concentrated. The sample was purified by silica gel column chromatography to obtain Compound G-1. (16.2 g, yield 85%, MS [M + H] < + > = 365)

Preparation of Compound G

Compound G-1 (15 g, 41 mmol), triphenylphosphine (8.5 g, 61.6 mmol) and o-dichlorobenzene (150 mL) were placed in a two-necked flask and stirred under reflux conditions for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, distilled under reduced pressure to remove the solvent, and extracted with CH ₂ Cl ₂ . The extract was dried over MgSO ₄ , filtered and concentrated. The sample was purified by silica gel column chromatography to give compound G (10.3 g, yield 75%, MS: [M + H] ⁺ = 333).

Production Example 8: Preparation of Compound H

Preparation of Compound H-1

Except that 11,11-dimethyl-11H-benzo [a] fluoren-5-yl) boronic acid was used instead of (7,7-dimethyl-7H-benzo [ (MS: [M + H] < ⁺ > = 365) was obtained in the same manner as the compound G-1.

Preparation of Compound H

Compound H was obtained in the same manner as Compound G except that Compound H-1 was used instead of Compound G-1 (MS: [M + H] ⁺ = 333).

Production Example 9: Preparation of Compound 1

3-necked flask, compound A (10g, 30mmol) and Compound a (10.7g, 36mmol) dissolved in xylene (200mL), sodium t- butoxide (4.3g, 45mmol) and Pd (P (t-Bu) 3) ₂ (0.3 g, 0.6 mmol) was added thereto, and the mixture was stirred under reflux in an argon atmosphere for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added, and the reaction solution was transferred to a separatory funnel. The extract was dried with MgSO ₄ and concentrated. The sample was purified by silica gel column chromatography to obtain Compound 1 (5.5 g, yield 31%, MS: [M + H] ⁺ = 594).

Production Example 10: Preparation of Compound 2

Compound 2 was obtained (MS: [M + H] ⁺ = 700) in the same manner as in the preparation of Compound 1, except that Compound b was used instead of Compound a.

Production Example 11: Preparation of Compound 3

Compound 3 was obtained (MS: [M + H] ⁺ = 644) in the same manner as in the preparation of Compound 1, except that Compound B was used instead of Compound A and Compound c was used instead of Compound a.

Preparation Example 12: Preparation of Compound (4)

Compound 4 was obtained (MS: [M + H] < ⁺ > = 594) in the same manner as in the preparation of Compound 1, except that Compound C was used instead of Compound A.

Production Example 13: Preparation of Compound 5

Compound 5 was obtained (MS: [M + H] ⁺ = 670) in the same manner as in the preparation of Compound 1, except that Compound C was used instead of Compound A and Compound d was used instead of Compound a.

Production Example 14: Preparation of Compound 6

Compound 6 was obtained (MS: [M + H] < ⁺ > = 578) in the same manner as in the preparation of Compound 1, except that Compound D was used instead of Compound A and Compound e was used instead of Compound a.

Production Example 15: Preparation of Compound 7

Compound 7 was obtained in the same manner as in the preparation of Compound 1 except that Compound D was used instead of Compound A and Compound f was used in place of Compound a. MS: [M + H] ⁺ = 628.

Production Example 16: Preparation of Compound 8

Compound 8 was obtained (MS: [M + H] < ⁺ > = 668) in the same manner as in the preparation of Compound 1, except that Compound E was used instead of Compound A and Compound g was used instead of Compound a.

Production Example 17: Preparation of Compound 9

Compound 9 was obtained (MS: [M + H] ⁺ = 644) in the same manner as in the preparation of Compound 1, except that Compound F was used instead of Compound A and Compound h was used instead of Compound a.

Production Example 18: Preparation of Compound 10

Compound 10 was obtained (MS: [M + H] < ⁺ > = 759) in the same manner as in the preparation of Compound 1, except that Compound F was used instead of Compound A and Compound i was used instead of Compound a.

Production Example 19: Preparation of Compound 11

Compound 11 was obtained (MS: [M + H] < ⁺ > = 594) in the same manner as in the preparation of Compound 1, except that Compound G was used instead of Compound A.

Production Example 20: Preparation of Compound 12

Compound 12 was obtained (MS: [M + H] ⁺ = 670) in the same manner as in the preparation of Compound 1, except that Compound G was used instead of Compound A and Compound j was used in place of Compound a.

Production Example 21: Preparation of Compound 13

Compound 13 was obtained (MS: [M + H] < ⁺ > = 759) in the same manner as in the preparation of Compound 1, except that Compound G was used instead of Compound A and Compound i was used instead of Compound a.

Production Example 22: Preparation of Compound 14

Compound 14 was obtained (MS: [M + H] ⁺ = 628) in the same manner as in the preparation of Compound 1, except that Compound G was used instead of Compound A and Compound k was used instead of Compound a.

Production Example 23: Preparation of Compound 15

Compound 15 was obtained in the same manner as Compound 1, except that Compound H was used instead of Compound A (MS: [M + H] < ⁺ > = 594).

≪ Comparative Example 1 &

A thin glass substrate coated with ITO (Indium Tin Oxide) at a thickness of 1,400 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. In this case, Fischer Co. was used as a detergent, and distilled water filtered by a filter of Millipore Co. was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

The following HI-A and hexaazatriphenylene (HAT-CN) were sequentially deposited by thermal vacuum deposition to a thickness of 800 Å and 50 Å, respectively, on the thus-prepared ITO transparent electrode to form first and second hole injection layers . The following HT-A was vacuum deposited to a thickness of 800Å to form a hole transport layer, and EB-A was thermally vacuum deposited thereon to a thickness of 600Å to form a hole control layer. Subsequently, a host RH-A and a dopant RD of 2 wt% were vacuum-deposited to a thickness of 400 Å to form a light emitting layer. Then, the following ET-A and Liq were thermally vacuum deposited at a weight ratio of 1: 1 to form an electron transport layer having a thickness of 360 ANGSTROM, followed by vacuum deposition of Liq to a thickness of 5 ANGSTROM to form an electron injection layer.

Magnesium and silver were sequentially deposited on the electron injection layer at a weight ratio of 10: 1 to a thickness of 220 Å and aluminum to a thickness of 1000 to form a cathode, thereby preparing an organic light emitting device.

≪ Examples 1 to 15 and Comparative Examples 2 to 8 >

The organic luminescent devices of Examples 1 to 15 and Comparative Examples 2 to 8 were formed into the same structure as that of Comparative Example 1, except that the compound described in Table 1 was used instead of RH-A in Comparative Example 1, Respectively.

Currents were applied to the organic light emitting devices fabricated in Examples 1 to 15 and Comparative Examples 1 to 8 to measure the driving voltage, current efficiency, and lifetime. The results are shown in Table 1 below. In this case, the driving voltage and current efficiency were measured by applying a current density of 10 mA / cm ² , and LT ₉₇ means the time until the initial luminance dropped to 97% at a current density of 20 mA / cm ² .

Host The driving voltage (V) Current efficiency (cd / A) LT ₉₇ (hr) Example 1 Compound 1 4.95 23.4 110 Example 2 Compound 2 4.91 23.2 105 Example 3 Compound 3 5.02 23.1 109 Example 4 Compound 4 4.93 23.0 115 Example 5 Compound 5 4.98 22.8 111 Example 6 Compound 6 5.06 22.9 101 Example 7 Compound 7 4.95 23.4 99 Example 8 Compound 8 4.97 22.5 106 Example 9 Compound 9 5.00 22.7 91 Example 10 Compound 10 5.08 22.1 104 Example 11 Compound 11 4.88 21.9 103 Example 12 Compound 12 4.85 21.4 90 Example 13 Compound 13 4.81 21.5 96 Example 14 Compound 14 4.86 21.7 91 Example 15 Compound 15 4.93 21.1 91 Comparative Example 1 RH-A 5.33 19.1 76 Comparative Example 2 RH-B 5.71 11.1 30 Comparative Example 3 RH-C 7.06 6.1 3 Comparative Example 4 RH-D 6.90 8.5 10 Comparative Example 5 RH-E 5.85 10.7 28 Comparative Example 6 RH-F 5.49 17.6 61 Comparative Example 7 RH-G 5.44 17.9 65 Comparative Example 8 RH-H 5.42 18.2 68

As can be seen from the results of Table 1, the structure in which the naphthalene ring is not present in the A or B ring in the structure of the formula (1), such as RH-B, has a high triplet energy.

In addition, in the case where the number of the nitrogen atoms is one in the unit serving as the upper electron receiver such as RH-C or RH-D, the pulling force of electrons is insufficient, which causes the voltage increase when applied to the device.

When C (CH ₃ ) ₂ is added to X3 or X4 as in RH-E, the stability of the material is deteriorated due to the steric hindrance between -CH ₃ and Ar of C (CH ₃ ) and the lifetime of the device is lowered.

When a compound having a structure represented by the formula (1) is applied to a host of a light emitting layer of an organic light emitting device, the device exhibits characteristics of low voltage, high efficiency, and long life.

1: substrate
2: anode
4: cathode
5: First hole injection layer
6: hole transport layer
7: Hole control layer
8:
9: Second hole injection layer
10: electron transport layer
11: electron injection layer

Claims (11)

A heterocyclic compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
One of X1 and X2 is CRaRb and the other is a direct bond,
Ra and Rb are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,
One of X3 and X4 is S or O and the other is a direct bond,
One of A and B is substituted or unsubstituted benzene and the other is substituted or substituted naphthalene,
Ar is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
R1 and R2 are the same as or different from each other, and each independently selected from the group consisting of deuterium; A halogen group; A nitrile group; A nitro group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; Substituted or unsubstituted -O (R10); Substituted or unsubstituted -Si (R11) (R12) (R13); A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; Or substituted or unsubstituted -N (R14) (R15), or is bonded to an adjacent group to form a ring,
R10 to R15 are the same or different from each other and each independently hydrogen; heavy hydrogen; An alkyl group; Or an aryl group,
a1 is an integer of 0 to 4; when a1 is 2 or more, R1 is the same as or different from each other,
a2 is an integer of 0 to 4, and when a2 is 2 or more, R2 is the same as or different from each other. The heterocyclic compound according to claim 1, wherein the formula 1 is represented by any one of the following formulas 2 to 4:
(2)

(3)

[Chemical Formula 4]

In the above formulas 2 to 4,
X1, X2, X3, X4, R1, R2, Ar, a1 and a2 are as defined in formula (1)
R3 to R6 are the same as or different from each other, and each independently selected from the group consisting of deuterium; A halogen group; A nitrile group; A nitro group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; Substituted or unsubstituted-O (R16); Substituted or unsubstituted -Si (R17) (R18) (R19); A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; Or substituted or unsubstituted -N (R20) (R21), or is bonded to an adjacent group to form a ring,
R16 to R21 are the same or different from each other, and each independently hydrogen; heavy hydrogen; An alkyl group; Or an aryl group,
a3 is an integer of 0 to 2, and when a3 is 2, R3 is the same as or different from each other,
a4 is an integer of 0 to 6, and when a4 is 2 or more, R4 is the same or different from each other,
a5 is an integer of 0 to 6, and when a5 is 2 or more, R5 are the same as or different from each other,
a6 is an integer of 0 to 6, and when a6 is 2 or more, R6 is the same as or different from each other. The heterocyclic compound according to claim 2, wherein the formula (2) is represented by any one of the following formulas (2-1) to (2-3):
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In the general formulas (2-1) to (2-3)
X1 to X4, R1 to R3, R6, Ar, a1 to a3 and a6 are as defined in formula (2). The heterocyclic compound according to claim 2, wherein the formula (3) is represented by any one of the following formulas (3-1) to (3-3)
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

In the above formulas (3-1) to (3-3)
X1 to X4, R1 to R4, Ar and a1 to a4 are the same as defined in formula (3). The heterocyclic compound according to claim 2, wherein the formula (4) is represented by any one of the following formulas (4-1) to (4-3)
[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

In Formulas 4-1 to 4-3,
X1 to X4, R1 to R3, R5, Ar, a1 to a3 and a5 are as defined in formula (4). The heterocyclic compound according to claim 1, wherein the compound represented by Formula 1 is represented by Formula 5 or Formula 6:
[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas (5) and (6)
X1 to X4, R1, R2, a1, a2 and Ar are as defined in the formula (1)
R7 to R9 are the same as or different from each other, and each independently selected from the group consisting of deuterium; A halogen group; A nitrile group; A nitro group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; Substituted or unsubstituted -O (R22); Substituted or unsubstituted -Si (R23) (R24) (R25); A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; Or substituted or unsubstituted -N (R26) (R27), or combine with adjacent groups to form a ring,
R22 to R27 are the same or different from each other and each independently hydrogen; heavy hydrogen; An alkyl group; Or an aryl group,
a7 is an integer of 0 to 4, and when a7 is 2 or more, R7 is the same as or different from each other,
a8 is an integer of 0 to 4, and when a8 is 2 or more, R8 are the same as or different from each other,
a9 is an integer of 0 to 4, and when a9 is 2 or more, R9 is the same as or different from each other. The heterocyclic compound according to claim 1, wherein the heterocyclic compound represented by the formula (1) is any one selected from the following heterocyclic compounds:

. An organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic compound layer disposed between the first electrode and the second electrode, wherein the organic compound layer comprises a heterocyclic compound according to any one of claims 1 to 7 Lt; / RTI > The organic light emitting device according to claim 8, wherein the organic material layer includes at least one of an electron injection layer and an electron transport layer, and at least one of the electron injection layer and the electron transport layer includes the heterocyclic compound. The organic light emitting device according to claim 8, wherein the organic layer includes a light emitting layer, and the light emitting layer comprises the heterocyclic compound. The organic electroluminescent device according to claim 8, wherein the organic material layer includes at least one of a hole injection layer, a hole transport layer, a layer that simultaneously transports and injects holes, and a hole control layer, and the hole injection layer, the hole transport layer, And at least one layer of the hole-transporting layer and the hole-transporting layer comprises the heterocyclic compound.

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